CN1149198C - Improved pyridine/picoline production process - Google Patents
Improved pyridine/picoline production process Download PDFInfo
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- CN1149198C CN1149198C CNB998152684A CN99815268A CN1149198C CN 1149198 C CN1149198 C CN 1149198C CN B998152684 A CNB998152684 A CN B998152684A CN 99815268 A CN99815268 A CN 99815268A CN 1149198 C CN1149198 C CN 1149198C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
Abstract
A process is provided for producing pyridine and/or alkylpyridine compounds comprising reacting a feedstream of ammonia and at least one C1-5 carbonyl reactant under conversion conditions and in the presence of a phosphorus-modified molecular sieve containing catalyst to produce a product stream having a pyridine and/or a pyridine based compound selected from alkylpyridines or polyalkylpyridines. The catalyst has improved attrition resistance without affecting catalyst activity or selectivity.
Description
Technical field
The present invention relates to utilize the phosphorus-containing catalyst that improves wear resistance, make improving one's methods of pyridine and/or picoline or other alkylation pyridine.
Background technology
Pyridine is for example a kind of important intermediate in weedicide and sterilant and the drug manufacture of agricultural chemicals, but also is the useful solvent in polymkeric substance and the textile industry.The important derivatives of pyridine comprises, for example nicotinic acid and nicotinamide (the basic life support element that HUMAN HEALTH is required), chlorobenzene Piao Er quick (a kind of antihistaminic agent), hexadecyl pyridinium salt (a kind of sterilant and sanitas), vazadrine (a kind of important antitubercular agent), and Paraquat (a kind of weedicide).
The pyridine that connects a methyl on ring texture is called picoline or picoline, and comprises 2-or α-Jia Jibiding, 3-or beta-picoline, and 4-or γ-picoline.
Pyridine and picoline can be used as the byproduct of coal-tar industry or coke production and obtain.Yet people only find a small amount of pyridine in coal tar, and the preferred method that obtains pyridine is to carry out chemosynthesis.Chemosynthesis generally relies on for example catalytic gas phase reaction of aldehydes or ketones (condensation) of ammonia (or amine) and carbonyl compound.Yet these chemical synthesis process always have the low and poor selectivity of yield, and working cycle and the short shortcoming of catalyst life.
At the pyridine chemical field, known term " alkali is synthetic " is used for discerning synthetic method, and by this method, process aldehyde and/or ketone and ammonia with the heterogeneous catalyst reaction, prepare the alkali and the alkyl derivative thereof of pyridine in gas phase.For example, in the presence of heterogeneous catalyst, aldehyde and ammonia is in 350 ° of-550 ℃ of reactions, obtains 2-and 4-picoline (α-and γ-picoline).An other example is acetaldehyde and formaldehyde energy and ammonia react, thereby acquisition pyridine and 3-picoline.This class pyridine synthetic method is described in for example U.S. Pat 4675410 and US 4220783.
Exist or do not exist under methyl alcohol and/or the formaldehyde, acetaldehyde or some other lower molecular weight aldehydes and ammonia react and obtain pyridine and alkyl derivative thereof, this reaction is finished containing in the presence of the soft silica-alumina compound of various promotors.Referring to, United States Patent (USP) for example, US 2807618 and US 3946020.Use back one class catalyzer, the yield of required product is very low always.Also synthesized alkyl pyridine, for example the report of being done in " catalysis progress " 18:344 page or leaf (Advances in Catalysislis18:344 (1968)) of nineteen sixty-eight synthesizes gaseous state acetaldehyde and ammonia by crystalline aluminosilicate NaX and H-mordenite.Though adopt these materials to make catalyzer, initial transformation efficiency height, catalyzer be through the rapid inactivation of coking, do not have a system of commercial appeal so provide, and it is a feature with bad catalytic stability.
The synthetic crystallization zeolite that discovery has medium hole dimension provides yield and the selectivity of product that commercial use is arranged, this hole dimension is determined as between 1 and 12 with the restricted index (Constraint Index) of zeolite, for example, have been found that ZSM-5 provides the yield and the selectivity of product of viable commercial.U.S. Pat 4220783 is pioneers of this discovery, it has instructed the synthetic of pyridine and alkyl pyridine, method is under effective reaction conditions, the ratio of aluminum oxide is being at least 12 by cadmium ion exchange and silicon-dioxide, restricted index (Constraint Index) containing in the presence of the crystalline aluminosilicate zeolitic catalyzer in the scope of 1-12, make ammonia and carbonyl reaction agent reaction, this reagent is the mixture of the aldehyde that contains 2-4 carbon atom, the ketone that contains 3-5 carbon atom or described aldehyde and/or ketone.
Instruction among U.S. Pat 4675410 and the US 4886179, in fluidized-bed or other removable bed bioreactor, use the ZSM-5 catalyst component, reaction by ammonia and carbonyl compound, pyridine synthesis, the preferred hydrogen that adds, whole catalyzer contains crystalline aluminosilicate zeolitic, and this zeolite is by group VIII metal ion exchanged in the periodictable.The silicon-dioxide of this crystalline aluminosilicate zeolitic is at least 15 to alumina molar ratio, is preferably 30-200, and restricted index (ConstraintIndex) is 4-12, ZSM-5 for example, and this processing provides the yield high and that select of pyridine.
U.S. Pat 5013843 instructions are in large scale continuous prod, to the aldehyde and/or ketone binary mixture interpolation the 3rd aldehydes or ketones that are used for preparing pyridine and alkyl substituted pyridines.In preferred system, propionic aldehyde is joined in the binary mixture of acetaldehyde and formaldehyde, so that produce β-pyridine and pyridine.Catalyzer for present method is the crystalline aluminosilicate zeolitic of restricted index 1-12 acid form, for example ZSM-5.
Put down in writing at " micropore and mesopore material (Microporous andMesoporous Material) " the 21st volume 447-451 page or leaf (1998) according to people such as Shimizu, use shows the selectivity that has increased pyridine with metal for example thallium, lead or cobalt improved ZSM-5 catalyzer.
But, although present progress is arranged, but still there are shortcoming in existing pyridine and picoline manufacture method, but though commercialization, but, and make pyridine, picoline or other alkylation pyridine with wear-resistant catalyst and will receive an acclaim because the loss of the catalyzer that causes of catalyst media bad mechanical strength causes the operating cost height.
U.S. Pat 5110776 discloses use carbamate additives for low phosphorus hydrochlorate and has handled zeolite catalyst, ZSM-5 for example, and it is as the additive of fluid catalytic cracking process (FCC), so that increase the output of octane in the olefin production.This parkerized catalyzer also has improved wear resistance except having improved catalytic performance.In U.S. Pat 5389232 and US 5472594, also described,, used the phosphorous modified ZSM-5 fluid catalyst as additional catalyst in order to increase the output of alkene among the FCC.
U.S. Pat 4380685 relates to the aromatic alkylation process of para-selectivity, comprises that the restricted index of this zeolite is 1-12 with the zeolite toluene methylation of ZSM-5 for example, and its with a kind of melts combine of phosphorus and chosen from Fe and cobalt.U.S. Pat 4554394 discloses the purposes of phosphorus processing zeolite catalyst, and it is used for strengthening para-selectivity at the aromatic product method for transformation.
Open in the International Application No. WO 98/14415, phosphorus is combined with molecular sieve and decatize, be used as effective control diffusivity and micro pore volume is reduced, and strengthen by toluene methylation selection manufacturing p-Xylol.
U.S. Pat 3,932 discloses in 431 to improving for the selectivity of 2-picoline and total yield, uses the amorphous catalytic material of phosphoric acid salt modification.
Be unexpectedly, have now found that, will be used for making the method for pyridine and/or picoline or other alkylation pyridine, the catalytic performance that reacts seldom or is not influenced, but improved the mechanical property of catalyzer through the molecular sieve catalyst that phosphorus is handled.
Summary of the invention
Therefore, the invention reside in a kind of manufacture method of pyridine and/or alkyl pyridine compound, this method comprises, under conversion condition and containing in the presence of a kind of catalyzer of molecular sieve and phosphorus, makes to contain ammonia and at least a C
1-5The product stream that contains pyridine and/or pyridine compounds and their is made in the stock liquid stream reaction of carbonyl reaction agent, and this pyridine compounds and their is selected from alkyl pyridine or poly-alkyl pyridine.
Therefore, the invention provides the manufacture method of pyridine or picoline or other alkylation pyridine or its merging thing, this method contains ammonia and at least a C by making
1-5The stock liquid of carbonyl reaction agent stream reacts in the presence of a kind of catalyzer, this catalyzer wear-resisting property raising and comprise molecular sieve catalyst and phosphorus.
The carbonyl reaction agent that the present invention uses is the hydrocarbon polymer that contains 1-5 carbon atom, and has a carbonyl moiety at least.The carbonyl reaction agent that participates in catalyzed reaction described herein can be formaldehyde, contain the aldehyde of 2-4 carbon atom, contain ketone or its mixture of 3-5 carbon atom.Representational aldehydes reagent comprises, acetaldehyde, propionic aldehyde, propenal, butyraldehyde and crotonic aldehyde.Representational ketone reagent comprises, acetone, methylethylketone, metacetone and methyl propyl ketone.This carbonyl reaction agent can exist with aqueous solution form, for example, formalin, it is the aqueous solution of formaldehyde, contains a spot of methyl alcohol and helps solubleness.The cosolvent that methyl alcohol or other alcohols also can be used as secondary process adds in the carbonyl reaction agent raw material.Methyl alcohol also can be used for the ventilation gas in the regeneration step, and people such as Shimizu are at Microporous and Mesoporolls Materials, and the 21st rolls up, and 447-451 page or leaf (1998) has disclosed this point.
The carbonyl reaction agent can comprise the mixture of two or more carbonyl compound.If the use mixture, each carbonyl component in the preferred mixture is according to predetermined the measuring now of all the other carbonyl component relatively.For example, when the mixture that at least a carbonyl reaction agent is formaldehyde and acetaldehyde, the preferred formaldehyde of these two kinds of components/acetaldehyde mol ratio content is 0.2-1.0, more preferably 0.4-0.8.In addition, the mixture of acetaldehyde and propenal generally can have acetaldehyde/propenal mol ratio of 0.7-1.25.Other carbonyl reaction agent composition can be prepared similarly, so that optionally control reaction product.Preferred carbonyl reaction agent contains the mixture of formaldehyde and acetaldehyde, and the primary product of reaction is pyridine and beta-picoline.
In this reaction mixture, the ammonia that is adopted is to the mol ratio (NH of carbonyl reaction agent
3/ CO) 0.5-30 normally, preferred 0.5-10, more preferably 1-5.
If desired, can add hydrogen (H to reaction
2), for example, with 0 (not adding hydrogen)-H
2/ carbonyl reaction agent (H
2/ CO) mol ratio is 5.0, the ratio of preferred 0.1-1.0 adds.
The reaction conditions that reacts between ammonia and at least a carbonyl compound comprises, 285 °-650 ℃ of temperature, preferred 340 °-550 ℃; Pressure 20-10000kPa (0.2-100 normal atmosphere), preferred 80-1000kPa (0.8-10 normal atmosphere); And weight hourly space velocity (WHSV) is 0.1-100, preferred 1-10.
The catalyzer that adopts in the inventive method comprises molecular sieve and phosphorus.Can merge to phosphorus in the molecular screen material, in the adhesive material or in molecular sieve and the tackiness agent.The preferred molecular sieve catalyzer is a crystalline, and is to have those of medium hole dimension, and this hole dimension is characterized by 1-12 with restricted index.Restricted index and measuring method thereof are described in U.S. Pat 4,016,218.Suitable medium hole dimension examples of molecular sieve comprises, ZSM-5 (U.S. Pat 3,702,886 and Re.29,948); ZSM-11 (U.S. Pat 3,709,979); ZSM-12 (U.S. Pat 3,832,449); ZSM-22 (U.S. Pat 4,556,447); ZSM-23 (U.S. Pat 4,076,842); ZSM-35 (U.S. Pat 4,016,245); ZSM-48 (U.S. Pat 4,397,827); ZSM-57 (U.S. Pat 4,046,685); And ZSM-58 (U.S. Pat 4,417,780).
Other useful catalysts material comprises, MCM-22 (U.S. Pat 4,954,325), MCM-36 (U.S. Pat 5,250,277), MCM-49 (U.S. Pat 5,236,575) and MCM-56 (U.S. Pat 5,362,697).SAPO-5, SAPO-11, SSZ-25, SSZ-31, SSZ-33, SSZ-35, SSZ-36, SSZ-37, SSZ-41, SSZ-42, ferrierite, X zeolite, zeolite Y and zeolite beta also are the examples of molecular screen material, they also can be used for the present invention.
Adopt the various adhesive materials of temperature and other condition in conjunction with the molecular screen material that adopts in the inventive method in available tolerance present method.This class material comprises activity and non-active material, for example, and clay, silicon-dioxide and/or metal oxide such as aluminum oxide.The latter can be natural generation or gelatinous precipitate or gel form, and it comprises the mixture of silicon-dioxide and metal oxide.Use active material, tend to change the conversion and/or the selectivity of catalyzer, therefore preferably do not use usually.Non-active material is suitable as the thinner of control inversion quantity in the given method, so that can obtain product economical and in an orderly manner, and does not need to adopt the means of other controls reaction speed.These materials can merge in the clay of natural origin, for example wilkinite and kaolin.Described material, promptly clay, oxide compound etc. play the tackiness agent effect of catalyzer.
Can comprise those of montmorillonite and kaolin group with molecular sieve compound natural source clay, these materials comprise and become that rock (subbentonites) takes off in class and usually with Dixie, McNamee, Georgia, the kaolin known with the Florida clay, perhaps the essential mineral composition is other material of halloysite, kaolinite, dickite, nacrite or anauxite.Suitable clay material comprises for example, wilkinite and diatomite.This class clay can be with the unprocessed state of initial recovery, or the state that experiences calcining, acid treatment or chemical modification at first uses.
Suitable crystalline molecular sieve can be the 1.0-90 weight % of this composition to catalyzer and tackiness agent or the total relative proportion of forming of carrier, preferred 5.0-70 weight %, and more preferably 20-60 weight %.
Can merge metal in the catalyzer of the present invention with hydrogenation-dehydrogenation effect.The appropriate amount of this function metal is the 0.001-10 weight % of this modified catalyst gross weight, preferred 0.005-5 weight %, more preferably 0.02-2 weight %.The example of suitable hydrogenation-dehydrogenation metal comprises the 8th, 9 and 10 family's metals (that is, Pt, Pd, Ir, Rh, Os, Ru, Ni, Co and Fe), the 7th family's metal (being Mn, Tc and Re), the 6th family's metal (be Cr, Mo and W), the 15th family's metal (being Sb and Bi), the 14th family's metal (being Sn and Pb), the 13rd family's metal (being Ga and In), the 11st family's metal (being Cu, Ag and Au) and the 12nd family's metal (being Zn, Cd and Hg).Preferred precious metal (being Pt, Pd, Ir, Rh, Os, Re, Ru, Mo and W).
Increase in order to produce required wear resistance, molecular screen material and/or adhesive material are combined with phosphorus, this combination or carry out separately or carry out with the combination of at least a oxide modifier, this oxide compound is preferably selected from the periodic table of elements (IUPAC version) IIA, IIIA, IIIB, IVA, IVB, the oxide compound of VA and VIA family element.Most preferably, described at least a oxide modifier is selected from the oxide compound of titanium, zirconium, boron, magnesium, calcium and lanthanum.The total amount of phosphorus and oxide modifier (if there is) is based on the element meter in the catalyzer, can be between 0.1 and 10 weight % of final catalyst weight, and preferably between 1.0 and 5 weight %.
The present invention contains the catalyzer that the wear resistance of molecular sieve and phosphorus is improved, and its wear resistance is measured by Dai Weixun index (Davison Index) wearing test.This Dai Weixun index wearing test is in U.S. Pat 3,650,988 and US 4,247,420 in carried out general description.
For catalyst system of the present invention, use jet cup available from Grace Davison, with 21 liters of/minute airflows, carry out 1 hour Dai Weixun index wearing test.In addition, in beginning Dai Weixun index wearing test of the present invention before specific 1 hour, with catalyzer of the present invention in 1000 (DI@ 1000) pre-treatment (calcining).
By U.S. Pat 4,356,338, the method described among US 5,110,776, US 5,231,064 and the US 5,348,643, can easily phosphorus be merged in the catalyzer of the present invention.By molecular screen material is contacted with suitable phosphorus compound solution individually or with tackiness agent or substrate material with merging, dry then also calcining can easily be finished with P contained compound and handle so that change phosphorus into its oxide form.Carried out 15 minutes to 20 hours for 25 ℃-125 ℃ in temperature with contacting generally of P contained compound.The concentration of phosphorus can be between 0.01-30 weight % in the contact mixture.
With after P contained compound contacts, can be dry and calcine this molecular screen material, so that phosphorus changes oxide form into.Can in rare gas element or in the presence of oxygen, calcine, for example,, in preferred 400-600 ℃ the air, carry out 15 minutes preferred 0.5-3 hour calcining at least at temperature 150-750 ℃.
Available similar techniques well known in the art merges to other modified oxide in the catalyzer of the present invention.
Can be used to the representative P contained compound that phosphorus oxide properties-correcting agent merges in the catalyzer of the present invention is comprised each derivative of organizing of following representative, PX3, RPX2, R2PX, R3P, X3PO, (XO) 3PO, (XO) 3P, R3P=O, R3P=S, RPO2, RPS2, RP (O) (OX) 2, and RP (S) (SX) 2, R2P (O) OX, R2P (S) SX, RP (OX) 2, RP (SX) 2, ROP (OX) 2, RSP (SX) 2, (RS) 2PSP (SR) 2 and (RO) 2POP (OR) 2, wherein, R represents alkyl or aromatic base, phenyl for example, and X is hydrogen, R or halogenide.These compounds comprise the primary, RPH2, the second month in a season, R2PH and uncle, R3P, phosphine is butyl phosphine for example, phosphine oxides, R3PO, for example tributylphosphine oxide compound, uncle's phosphine sulfide, R3PS, the primary, RP (O) (OX) 2, the second month in a season, R2P (O) OX, phosphonic acids, for example phosphenylic acid, corresponding sulfur derivatives, for example RP (S) (SX) 2 and R2P (S) SX, phosphonic ester, for example dialkyl alkylphosphonate, (RO) 2P (O) H, phosphonic acids dialkyl group alkyl ester, (RO) 2P (O) R and alkyl dialkylphosphinic salts, (RO) P (O) R2; Phosphinous acid, R2POX, for example diethyl trivalent phosphoric acid, the primary, (RO) P (OX) 2, the second month in a season, (RO) 2POX, and uncle, (RO) 3P, phosphite, with and ester, for example a propyl diester, alkyl dialkylphosphinic acids ester (alkyldialkyl phosphinites), (RO) PR2 and dialkyl group alkyl sub-phosphonate (dialkylalkyphosphinite), (RO) 2PR, ester.Also can adopt corresponding sulfur derivatives, it comprises (RS) 2P (S) H, (RS) 2P (S) R, (RS) P (S) R2, R2PSX, (RS) P (SX) 2, (RS) 2PSX, (RS) 3P, (RS) PR2 and (RS) 2PR.The example of phosphorous acid ester comprises, tricresyl phosphite methyl ester, tricresyl phosphite ethyl ester, phosphorous acid diisopropyl ester, phosphorous acid butyl ester and for example, the pyrophosphite of tetraethyl-pyrophosphite etc.Alkyl in the described compound preferably contains 1-4 carbon atom.
Other suitable P contained compound comprises ammonium hydrogen phosphate, Phosphorates phosphorus Halides is phosphorus trichloride for example, bromide and iodide, dichloro-alkyl phosphate (alkyl phosphorodichloridites), (RO) PCl2, chloro phosphate dialkyl ester (dialkylphosphoro-chloridites), (RO) 2PCl, chloro dialkyl alkylphosphonate (dialkylphosphinochloroidites), R2PCl, alkyl chloride is for alkyl phosphonates (alkyl alkylphosphonochloridates), (RO) (R) P (O) Cl, dialkyl group phosphino-chlorine (dialkyl phosphinochloridates), R2P (O) Cl and RP (O) Cl2.The corresponding sulfur derivatives that is suitable for comprises (RS) PCl2, (RS) 2PCl, (RS) (R) P (S) Cl and R2P (S) Cl.
Concrete P contained compound comprises ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, chlorophosphonazo diphenylurea, trimethyl phosphite, phosphorus trichloride, phosphoric acid, Phenylphosphine acyl chlorides, trimethyl phosphite 99, phenylbenzene phosphinous acid, diphenyl phosphonic acid, chlorothio diethyl phosphoric acid, methyl acid phosphate and other alcohol-P
2O
5Reaction product.
Can be used for the representative boron-containing compound that boron oxide properties-correcting agent merges in the catalyzer of the present invention is comprised boric acid, trimethyl borate, boron oxide, sulfuration boron, hydroborons, dimethoxy butyl boron (butylboron dimethoxide), butyl boron dihydroxide, dimethyl boron trioxide, hexamethyl borazole, phenyl-boron dihydroxide, boron triethyl, diborane and triphenyl-boron.
With reference now to following examples,, the present invention is described in more detail.
Embodiment
The comparative example 1
Conventional catalyst by spraying drying and calcining slurry manufacturing pyridine/picoline production usefulness is created in the catalyzer that comprises ZSM-5 in silica-alumina-clay matrix.Zeolite is 35: 65 to the weight ratio of tackiness agent, and the silicon-dioxide of this ZSM-5 zeolite: alumina ratio is 55: 1.
Embodiment 2
Repeat Preparation of catalysts program among the comparative example 1, and the phosphoric acid of 1 weight part added in the catalyst mixture of 10.3 weight parts, thereby obtain the phosphorus-containing catalyst of phosphorous 2.8 weight % (based on the element meter), this catalyzer is contained in the ZSM-5 in silica-alumina-clay matrix.
Embodiment 3
Use above-mentioned Dai Weixun index (Davison Index) wearing test, promptly DI@1000 estimates the catalyzer of comparative example 1 and embodiment 2.Phosphorus is improved to 10 of embodiment 2 phosphorus modified catalysts with the wear resistance of catalyzer from comparative example 1 25.The improved wear resistance of lower value representation.
Embodiment 4
Estimate the catalytic performance of comparative example 1 and embodiment 2 catalyzer.Data are listed in table 1.
Table 1
| Catalyzer | Embodiment 1 | Embodiment 2 |
| Test condition | ||
| The catalyzer add-on, gram | 450 | 450 |
| Average reaction temperature, ℃ | 450 | 455 |
| Working time, hour | 7 | 8 |
| The mass balance cycle, hour | 7 | 8 |
| Combined feed total feed, gram | 1342.35 | 1621.3 |
| Acetaldehyde | 384.42 | 464.55 |
| Formaldehyde | 249.85 | 301.71 |
| Water | 391.66 | 472.95 |
| Methyl alcohol | 33.76 | 40.77 |
| Ammonia | 282.66 | 341.3 |
| The gross product of collecting, gram | 1264.5 | 1525.0 |
| Unreacted aldehyde is in HCHO | 14.16 | 17.08 |
| Ammonia+alkylamine | 173.86 | 217.0 |
| Pyridine | 172.35 | 206.0 |
| α-Jia Jibiding | 0.51 | Do not have |
| Beta-picoline+γ-picoline | 82.95 | 98.66 |
| Water | 682.32 | 819.23 |
| Highly basic (Heavy bases)+neutral oil | 138.35 | 167.03 |
| Carbon on the % catalyzer | 3.96 | 4.09 |
| % mass balance thing | 95.53 | 95.20 |
| The molecular fraction of yield | ||
| Pyridine | 49.90 | 49.28 |
| Beta-picoline | 20.37 | 20.09 |
| Add up to | 70.27 | 69.38 |
| Pyridine/beta-picoline (weight ratio) | 2.07 | 2.08 |
Embodiment 3 and 4 result show fairly obviously, in view of its certified catalytic activity, when pressing i) pyridine yield, ii) beta-picoline yield and iii) during the selective determination catalytic performance of pyridine/beta-picoline, although wear resistance remarkably improves, the phosphorus that is added does not influence catalyst performance.
Claims (10)
1. method of making pyridine and/or methyl-pyridyl compound, it is included under the conversion condition and in the presence of the catalyzer of the P contained compound that contains molecular sieve and oxide form, makes to contain ammonia and C
1-5The reaction of the stock liquid of carbonyl reaction agent stream contains pyridine and/or based on the product stream of the compound of pyridine with manufacturing.
2. according to the process of claim 1 wherein that described P contained compound is selected from ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, trimethyl phosphite, phosphoric acid, Phenylphosphine acyl chlorides, trimethyl phosphite 99, phenylbenzene phosphinous acid, diphenyl phosphonic acid, chlorothio diethyl phosphoric acid and methyl acid phosphate.
3. according to the method for claim 2, wherein, described conversion condition comprises temperature 285-650 ℃ and pressure 20-10000kPa.
4. according to the method for claim 2, wherein, described molecular screening is from ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ZSM-58, MCM-22, MCM-36, MCM-49, MCM-56, SAPO-5, SAPO-11, SSZ-25, SSZ-31, SSZ-33, SSZ-35, SSZ-36, SSZ-37, SSZ-41, SSZ-42, ferrierite, zeolite beta, X zeolite and zeolite Y.
5. according to the method for claim 4, wherein said molecular sieve is ZSM-5.
6. according to the method for claim 2, the weight percentage of P contained compound is in the scope of 0.1-10 in the wherein said molecular sieve catalyst.
7. according to the method for claim 2, wherein the carbonyl reaction agent contains formaldehyde and/or acetaldehyde.
8. according to the method for claim 6, wherein, measure when pressing DI@1000, this wear resistance is not more than 20.
9. according to the method for claim 6, wherein, measure when pressing DI@1000, this wear resistance is not more than 10.
10. according to the method for claim 2, wherein described P contained compound is merged in this molecular sieve.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/223,658 US5994550A (en) | 1998-12-30 | 1998-12-30 | Pyridine/picoline production process |
| US09/223,658 | 1998-12-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1332728A CN1332728A (en) | 2002-01-23 |
| CN1149198C true CN1149198C (en) | 2004-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998152684A Expired - Lifetime CN1149198C (en) | 1998-12-30 | 1999-11-09 | Improved pyridine/picoline production process |
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| Country | Link |
|---|---|
| US (1) | US5994550A (en) |
| EP (1) | EP1140843B1 (en) |
| JP (1) | JP5016751B2 (en) |
| CN (1) | CN1149198C (en) |
| AT (1) | ATE335727T1 (en) |
| DE (1) | DE69932739D1 (en) |
| TW (1) | TW460463B (en) |
| WO (1) | WO2000040556A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8049275B2 (en) | 1998-11-17 | 2011-11-01 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device |
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| CA2552158C (en) * | 2003-12-31 | 2010-06-22 | Council Of Scientific & Industrial Research | Catalyst for synthesis of 2- and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst |
| US20050215433A1 (en) * | 2004-03-26 | 2005-09-29 | Benitez Francisco M | Aromatic fluid as agricultural solvent |
| CN100460393C (en) * | 2006-11-21 | 2009-02-11 | 浙江大学 | 2,Process for preparing 3-dimethylpyridine |
| US8846559B2 (en) * | 2008-11-03 | 2014-09-30 | Saudi Basic Industries Corporation | Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing |
| CN101612592B (en) * | 2009-07-21 | 2011-12-14 | 上海化工研究院 | Preparation method of low abrasion microsphere catalyst produced in situ |
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-
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- 1998-12-30 US US09/223,658 patent/US5994550A/en not_active Expired - Lifetime
-
1999
- 1999-11-09 DE DE69932739T patent/DE69932739D1/en not_active Expired - Lifetime
- 1999-11-09 WO PCT/US1999/026359 patent/WO2000040556A1/en active IP Right Grant
- 1999-11-09 CN CNB998152684A patent/CN1149198C/en not_active Expired - Lifetime
- 1999-11-09 AT AT99956962T patent/ATE335727T1/en not_active IP Right Cessation
- 1999-11-09 JP JP2000592265A patent/JP5016751B2/en not_active Expired - Fee Related
- 1999-11-09 EP EP99956962A patent/EP1140843B1/en not_active Expired - Lifetime
- 1999-12-15 TW TW088121985A patent/TW460463B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8049275B2 (en) | 1998-11-17 | 2011-11-01 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device |
| US8680532B2 (en) | 1998-11-17 | 2014-03-25 | Semiconductor Energy Laboratory Co., Ltd. | Method of fabricating a semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000040556A1 (en) | 2000-07-13 |
| DE69932739D1 (en) | 2006-09-21 |
| JP2002534413A (en) | 2002-10-15 |
| CN1332728A (en) | 2002-01-23 |
| EP1140843A4 (en) | 2002-05-02 |
| EP1140843B1 (en) | 2006-08-09 |
| US5994550A (en) | 1999-11-30 |
| EP1140843A1 (en) | 2001-10-10 |
| TW460463B (en) | 2001-10-21 |
| JP5016751B2 (en) | 2012-09-05 |
| ATE335727T1 (en) | 2006-09-15 |
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